DE2720792A1 - TRIAZOLOTRIAZINE DERIVATIVES, METHOD FOR PREPARING THE SAME AND CONTAINING HERBICIDALS AND WEED CONTROL METHODS - Google Patents

Description

ψ Dipl.-Chem. Bühling

9 7 9 Π 7 Q 9 Dipl.-lng. Chins

& I l. \ JI zl £. Din! -Inn. Green

Dipl.-Ing. Group

Bavariarlng 4, Postfach 20 24 03 8000 Munich 2

Tel .: (0 89) 53 96 53-56

Telex: 5 24 845 tipat

cable. Germaniapatent Munich

May 9, 1977 B 8170 / case PP 28774

IMPERIAL CHEMICAL INDUSTRIES LIMITED London, United Kingdom

Triazolotriazine derivatives, processes for producing the same and herbicidal compositions containing them, and also Weed control procedures

709847/0982

Dresdner Bank (Munich) Account 3939 844 Postscheck (Munich) Account (70-43-604

B 8170

5 - 2720702

The invention relates to herbicidal triazolotriazine derivatives and their preparation, as well as herbicidal compositions and weed control methods containing them.
5

The method of the present invention for seriously damaging or killing unwanted plants is thereby characterized in that one triazolotriazine compound on the plants or the growth medium for them of the general formula (I):

R ¹

V ¹ V ⁰

HN

or a salt thereof applies, where R is an alkyl or cycloalkyl radical with 1 to 8 carbon atoms

2
and R stands for a hydrogen atom, an alkyl or cycloalkyl radical with 1 to 6 carbon atoms, an alkylthio radical with 1 to 6 carbon atoms or a dialkylamino radical, where the alkyl radicals can each contain 1 to 6 carbon atoms.

If R is an alkyl radical, this can, for example, be a straight or branched chain alkyl radical or a Be cycloalkyl. For example, R can be replaced by methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, cyclopentyl, neopentyl or cyclohexyl are formed. Preferably R is an isopropyl,

ρ sec-butyl or cyclopropyl radical. When R is an alkyl radical is, this can be, for example, a straight or branched chain alkyl radical or a cycloalkyl radical. So can

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R, for example, for methyl, ethyl, propyl, isopropyl, Cyclopropyl, butyl, sec-butyl, tert-butyl or isobutyl stand.

Preferred compounds for use in the method of the invention include those where R is an isopropyl radical. For specific examples of preferred compounds when used in accordance with the invention include the compounds No. 1 and 4 of the following Table I.

The compounds of the general formula (I) contain an N-H group. The hydrogen atom of this group is acidic and can be replaced by salt-forming bases such as alkali or alkaline earth metal cations be. Correspondingly, the compounds of the formula (i) can, for example, be broken down into their sodium, potassium, Calcium or magnesium salts are converted. For more examples of cations that are used to generate Salts of compounds (i) that can be used include the ammonium ion and substituted ammonium ions such as with one, two, three or four alkyl radicals substituted with 1 to 6 carbon atoms each Ammonium ions. Preferred cations are sodium and

25 potassium cations.

The structural formula (i) given above is used to represent the structure of those used in accordance with the invention Connections viewed as the most appropriate. However, compounds of this type are in principle capable of at least to exist in an alternative tautomeric form, which has the following formula (II):

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R ¹

(ID

N N \ o

It can therefore be assumed that the formula (I) mentioned at the outset, all tautomeric structures such as (II) encloses and is representative of this.

Specific examples of compounds used in the invention Procedures useful are set out in Table I below.

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CD OO

O CO 00 N>

TABLE I.

^H "Y

Connection no. R ¹ R ² Melting point ° c 1 iso C ₁ H _n iso C ₀ H _n 156-159 2 CH iso C ₁ H _n 214 3
4th
5 C ₃ H ₇
iso C ₃ H ₇
iso C ₁ H _n iso CH 112
202
185 6th
7th
8th iso CH CH ₃
C ₂ H 175
225
157 9
10
11 C ₃ H ₇
^C 2 ^H 5 C ₃ H ₇
CH ₃
iso C ₁ H _n 236
over 260
125 C ₂ H ₅
cyclo C, H ₁₁
sec C ₄ H ₉ CH ₃
CH ₃
C ₂ H ₅

03 I.

-J CO N)

TABLE I (r orte.)

Connection Mr. R ¹ R ² Melting point ⁰ C 12th iso C.H " iso C ₁ H ₁ 145 13th neo CcH ₁ , CH 194 14th sec CH j
CH 160 15th neo Cj-H _{1 λ} j
CH 171 16 iso CH _Q ZJ
^C 2 ^H S 125 17th neo Cj-H ₁ , iso C ₅ H-, 186 18th Cyclo propyl iso C _O H_, 154 19th Isopropyl y /
H 216 20th Isopropyl t C ₄ H ₉ 128 21 sec C ₄ H ₉ i ^C 4 ^H 9 139 22nd sec C ₄ H ₉ iso C _O H_ 125 23 cyclo C ₀ H ₁ .
- ■ * jb iso C ₃ H ₇ 217 24 iso C ₃ H ₇ CH ₃ S- 260 25th iso C ₀ H-, (CH ₃ ) ₂ N- 220

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The compounds used in the method according to the invention include those which are undesirable plants seriously damage or destroy if applied directly to plants ("post-germination application") and when applied to soil or other growth media, undesirable seedling emergence Prevent plants ("pre-germination application"). Those for serious harm or destruction The amount of application required for undesired plants depends on the nature of the plants and the application the particular compound chosen. However, quantities of 0.5 to 10 kg / ha are indicative to be mentioned as generally suitable, with 1 to 4 kg often being preferred.

When used directly on plants (i.e. after germination), those in the method according to the invention used compounds are relatively less phytotoxic to cultivated cereals (such as maize, Wheat and barley) than against many other plant species. Accordingly, the compounds can be used for control of weed growth in cereal crops.

In addition to controlling broadleaf weeds, the compounds of the invention also exhibit one harmful herbicidal effects on wild oats at application rates which wheat or barley are not significantly affect. According to a further aspect, the invention therefore comprises a method for selective Inhibition of the growth of weeds, including wild oats, in crops of wheat and barley, in which on the Cultivated area a triazolotriazine compound of the formula (I) in an amount sufficient to inhibit weed growth is applied, however, for an essential

'' ■■ ι -.- ι.Ί. -Ι::>; 2

- 11 -

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Damage to the crops is insufficient. The rate or amount at which the compound is to be applied will depend on the particular compound chosen for the application, but a lot of can be used as a guide 0.5 to 5 kg / ha can be considered generally suitable.

A particularly preferred compound for the control of wild oats in wheat or barley is the compound no. 4 of Table I.
10

The compounds used according to the invention can also be used as selective herbicides for weed control can be used in peanut crops when applied early in the growth of the peanut plants will.

The compounds used according to the invention are preferably applied in the form of a composition in which the active ingredient is mixed with a diluent or carrier. According to a further aspect of the invention, herbicidal compositions are therefore provided which have, as an active ingredient, a compound of the formula (I) or a metal, ammonium or substituted ammonium salt thereof, mixed with a solid or liquid diluent. The herbicidal compositions preferably also contain a surface-active agent.

The solid compositions according to the invention can, for example, be in the form of dusting powders or in granular form or as granules. Suitable solid diluents include, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, magnesia powder and fuller's earths.

35 Solid compositions can also be in the form of

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dispersible powders or granules are present, which in addition to the active ingredient a wetting agent for relief the dispersion of the powder or granules in liquids. Such powders or granules can Include fillers, suspending agents, and the like.

Liquid compositions include aqueous solutions, dispersions and emulsions that contain the active ingredient preferably contained in the presence of one or more surface-active agents. A form of liquid Composition according to the invention comprises an aqueous solution of an alkali metal salt of a triazolotriazine compound of the type mentioned. The selection of a surfactant for the compositions of the invention falls within the competence of a herbicide specialist. However, as an example it can be mentioned that Ready-to-use sprays for use in the field have been produced that contain an aqueous solution of the sodium salt of compound no. 4 of Table I with a content of 1 g / l "Ortho X-77" (a mixture of surface-active Agents containing alkylaryl polyoxyethylene glycols together with free fatty acids and isopropanol) exhibit. A spray with the sodium salt of compound no. 4 in water at a content of 6 g / l "Atplus" was also made ("Atplus" is a a herbicide additive comprising emulsifiable oil). The liquid compositions according to the invention can also one or more corrosion inhibitors such as e.g.

Contain 30 laurylisoquinolinium bromide.

Surfactants can be of the cationic, anionic or nonionic type. To suitable Cationic type agents include, for example, quaternary ammonium compounds such as cetyltrimethyl-

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ammonium bromide. To suitable agents from the anionic Type include for example soaps, salts of aliphatic monoesters of sulfuric acid such as sodium lauryl sulfate and salts of sulfonated aromatic compounds such as dodecylbenzenesulfonate, sodium, calcium and Ammonium lignosulfonate, butyl naphthalene sulfonate and a mixture of the sodium salts of diisopropyl and triisopropyl naphthalene sulfonic acid. Suitable agents of the non-ionic type include, for example, the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol or with alkylphenols such as octylphenol, Nonylphenol and octyl cresol. Other non-ionic agents are the Partlalester, which differ from long-chain Fatty acids and hexose anhydrides, such as to derive

15 Example of sorbitol monolaurate, the condensation products

the said partial esters with ethylene oxide and the lecithins.

The compositions to be used in the form of aqueous solutions, dispersions or emulsions are generally supplied in the form of a concentrate which contains a high proportion of active ingredient and which is diluted with water before use. These concentrates should usually be storable for longer periods of time and, after such storage, should be dilutable with water to form aqueous preparations which remain homogeneous for a sufficient period of time so that they can be dispensed with a conventional spray arrangement. In general, concentrates can conveniently contain 10 to 85% and preferably 25 to 60 % by weight of active ingredient. Ready-to-use diluted preparations can contain different amounts of active ingredient, depending on the intended use; however, dilute preparations suitable for many purposes contain between

35 0.01 and 10 %, preferably between 0.1 and 1% by weight of active ingredient.

7 ί! y ö 4 7/0 Β 8 2

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According to a further aspect, the invention comprises herbicidally active triazolotriazine compounds of the formula (I) and salts thereof.

The compounds (i) provided according to the invention can be prepared according to reaction scheme (A) below will:

Scheme A

10 _R 1

0 '0 N N

V ¹¹ Y

0 0

V ¹¹ Y

Cl OR ^ NH ₂ ^ f

(IV) (III)

According to scheme A, an N-substituted N-chlorocarbonyl urethane derivative is used (IV) reacted with a 5-substituted 3-amino-1,2,4-triazole (III). The reaction takes place preferably in an inert diluent or solvent for the reactants.

The N-chlorocarbonyl derivative is made by reaction

1 3

a urethane R NCOR with phosgene in a diluent, 0

preferably made in toluene. The radical R has the meaning already given. R stands for one lower alkyl radical, preferably a methyl group. The triazole derivative ($ 11 can be a known compound be produced by processes analogous to those used for known compounds, both

2 for example by reacting a carboxylic acid R COOH

35 with an aminoguanidine according to the following equation:

711984 7/0 9 82

B 8170

ρ N ~ N

R ^ C-OH + NH ₀ NH-C-NH ₉ > U >. _O

0 NH ^wn 2 u

The structure of the products prepared according to Scheme A was confirmed by preparing Compound No. k of Table I by an alternative unique process route and establishing the identity of the product with Compound No. U prepared according to Scheme A.

An alternative suitable method for preparing the compounds of the invention is provided below shown in scheme B:

Scheme B

N-N

Jl V

3R ¹ NCO> (I) + R ¹ NHCNHR ¹

H υ

According to scheme B, a suitably substituted 3-amino-1,2,4-triazole is reacted with three times the molar amount of an appropriate isocyanate to form the compounds (I) which are used according to the invention. In Scheme B above, the symbols have R and

2
R has any of the meanings already mentioned. The reaction according to scheme B is preferably carried out in a diluent. Examples of diluents include pyridine and alkyl pyridines. The reaction takes place

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preferably at an elevated temperature of for example 100 to 150 ° C. The reaction can suitably be carried out at the boiling point of pyridine (ie at about 115 ^° C.).

Another procedure for preparing the compounds according to the invention is shown in Scheme C.

Scheme C

R ¹

N N

(V)

According to scheme C, a suitably substituted 3-amino-1,2,4-triazole with a bis [chloroformyl] compound (V) implemented. The reaction is preferably carried out in an inert diluent or solvent for the reactants. Examples of diluents include liquid hydrocarbons such as for example toluene and aprotic solvents such as acetonitrile.

The invention is illustrated below by means of examples in which all parts are by weight and all temperatures are given in degrees Celsius, unless otherwise stated.

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example 1

This example shows the herbicidal properties of the compounds used in the process according to the invention. All compounds (0.12 g) were prepared for the test by mixing with 5 ml of an emulsion, by diluting 100 ml of a 21.8 g / l "Span 80" and 78.2 g / l "Tween 20" in methylcyclohexanone containing solution to 500 ml (with water). "Span 80" ^ is a surfactant with sorbitan monolaurate. "Tween 20" ^ is a surfactant Agent with a condensate of 20 molar parts of ethylene oxide with sorbitan monooleate. The mix of Compound and emulsion were shaken with glass beads

15 and diluted to 12 ml with water.

The spray prepared in this way was applied to young potted plants (test after germination) in the Table II below in a 1000 l / ha (10 kg triazine compound per hectare) equivalent Amount sprayed on. The damage to the plants was determined 14 days after spraying by comparison with untreated Plants tested and the result graded from 0 to 3, with 0 no effect and 3 a 75 to 100% destruction means. When testing for herbicidal effectiveness before germination seeds of the test cultivars were placed on the surface of fiber troughs with soil and with the compositions sprayed in quantities of 1 000 l / ha. The seeds were then covered with more soil. Three weeks after spraying the seedlings or seedlings in the sprayed fiber troughs with seedlings in unsprayed Control troughs were compared and the damage classified according to the same scale. The results are in the

35 summarized below in Table II.

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TABLE II

CD OC

CD CC 00

link Application before
("pre") or after
("post") d. Germinator TEST PLAN Z en Le To Ot / A v Dg Pr Cp 2 Pre
post 0
2 1
0 0
0 2
2 1
0 0
0 3 post 2 3 0 0 0 0 4th Pre
post 2
3 (N ro 0
3 3
2 0
2 1
1 5 post 3 3 2 0 0 0 6th post 3 3 0 0 0 0 7th Pre
post ro ro 1
1 1
0 1
0 0
0 0
0 8th Pre
post ro ro 1
3 0
1 1
0 0
0 0
0

00 I.

ro

TABLE II (cont. )

CD CO OO NI

link
No. Application before
(pre) or after
(post) ά. Germinate TEST PLANTS Le To Ot / Av Dg Pr Cp 9 Pre
post 0
3 0
2 0
0 0
0 0
0 3
0 10 Pre
post 0
3 0
1 0 0
0 0
0 0
0 11 Pre
post 0
3 0
3 0
0 0
0 0
0 0
0 12th post 3 3 0 3 1 0 13th post 3 3 1 1 1 0 14th post 3 3 2 3 2 0 15th post 1 3 0 3 1 0 16 post 2 3 0 0 0 0 17th post 1 3 0 3 0 0

TABLE II (cont.)

O CO CD

link
No. Application before
(pre) or after
(post) d. Germinate TEST PLANTS Le To Ot / Av Dg Pr Cp 18th post 3 3 0 2 2 0 19th post 2 3 2 1 0 0 20th Pre
post U) U) 1
3 0
1 3 3
2 0
0 21 * Pre
post ro ro 0
3 0
3 2 0
1 0
0 23 post 3 3 - - 0 0 24 post 3 3 0 - 0 0 25th Pre
post 1
0 0
3 2
2 0
2 0
0

* 5 kg / ha applied

IO

(O

03 3

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Compounds 3, 5, 6, 10 to 19, 21 and 22 to 25 show no significant herbicidal in the pre-germination test Effectiveness.

The following abbreviations were used for the test plants:

Le Salat To Tomato

Ot / Av cultivated oats and wild oats ( Avena fatua),

Wild oats were used in the post-germination test and cultivated oats in the pre-germination test .

Dg Digitaria sanguinalis

15 Pr Perenne ryegrass ( Lolium perenne ) Cp Cyperus rotundus

Example 2

This example shows the herbal properties of compounds used according to the invention with respect to a broader test plant range than in example 1. The tests were carried out in a manner similar to that in example 1, but using lower application amounts. The compounds were prepared by mixing the appropriate amount of each compound with 5 ml of an emulsion obtained by diluting 160 ml of a 21.8 g / l "Span 80" and 78.2 g / l "Tween 20" in methylcyclohexanone Solution with water to 500 ml had been obtained. The compound and emulsion mixture was shaken with glass beads and diluted to 40 ml with water. The damage to the plants was noted according to a rating from 0 to 5, where 0 means damage of 0 to 20 % and 5 means complete destruction. In the tabulated results, (-) means that no test was performed. Table III shows the results obtained. 709847/0982

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it O CO CO CO ο O I. ι O ι O O O O ' O U
ω £ Λ) O Λί 5
• r-l I O · <* O O O H O O ' • ro m 4Y
W. N H ί O in CN O O i-H <-i O O O O r-H 3
CU O ro O O O O O I. ι O O S ¹ O r-l r-t O O O O O t-i O O O P, -H-w 3 Verb. O CN 1· in O r-H O O CS r-l CM 4-1 O J, CN • vT I. I. ro I. CS CS CS CS I. S. CJ
3 CN in in • vT in CN _, 1· O in 2 O ι in in O ro in "■ * m in U.
α. O in ro in O m • vT in <s · » m Ε « -H ω CU ■ vT ^ • "3 · in f-l in ro ro r-t ro in Ej M. CS <* CN rH ro CS I. I. ro in C. O in ro O in O <* CS in • -I r-4 • Ι · U CN in ro O in CN in ro r-l O in S. O η CS ro O O O O ■ vT Η " O O N
S. O O ro ro CN CS O O > I. CM O cn O O O O O O O O O O O O 4Y
υ (N ro * O CN O 1· O ro ro H rr O CN O CN O ro O I. I. O <* « CN T O CS O r- \ I. I. ■ 0 · in Λ
CO CN m in in m O CS in in JJ 4Y yy JJ JJ JJ yy U) U) (U a) V) ω Ul approx cn cn a) cn 0 O U U O U O O O O U O CU CU CU CU CU CU CU CU CU CU CU CU m r-t in in in in m in r-l in in m ro ■ 3 · in co σ » in CD
r-l

7 U 9 ü U 7/0 9 8 2

tab, in (cont. )

Verb.
No. Applica
tion rate
(kg / ha) Before or
Post-germination
test Sb Rp Ct Sy Mz Ww Rc Sn ip At the TEST PLANTf fi Approx Po away Cv Ot / wk Dg Pooh St. Ec Sh Ag Cn 6th 0.05 Pre 5 0 0 0 0 4th O 2 0 2 pi 0 0 2 - 1 1 1 2 1 - - 0 post 3 3 3 3 0 O O 5 3 3 1 4th 0 5 0 O 0 0 O 0 0 0 0 11 0.05 Pre 5 2 0 1 1 0 3 3 3 - 4th 0 0 1 - O 1 1 1 1 - 0 0 post 4th 5 4th 3 O 0 0 5 5 5 0 5 - 5 5 O 3 1 4th 4th 3 0 0 12th 0.05 Pre 0 0 0 0 O - O 0 0 0 4th 0 0 O - O O 0 O 0 - 0 0 -J post 2 - - 3 O - 3 3 3 - 0 4th 5 2 2 O O - O - O 0 0 O
CD
OO
* ^
-J 20th 5.0 Pre 5 2 4th 4th O 1 0 3 2 0 2 2 5 5 - O O 0 1 1 - - 0 / 0982 post 5 4th 5 4th 2 2 4th 5 5 5 4th 5 5 5 5 3 3 3 5 5 3 2 0 21 5.0 Pre 4th 0 0 O O 0 0 0 0 0 5 1 0 5 - 0 0 0 0 0 O 0 O post 5 - 3 4th 1 2 1 5 5 4th O 4th 5 5 5 3 3 3 3 4th - 1 0 22nd 5.0 Pre O 0 O 0 0 O 0 O 0 0 5 O 2 3 - 0 2 2 1 0 O 0 O post 4th 4th 4th 4th 0 2 2 5 4th 4th 1 4th 3 3 4th 2 1 2 0 2 0 O O 23 4.0 Pre 4th O 0 0 O O O 0 0 0 4th 0 0 O - 0 0 - 0 0 0 0 0 post 5 4th O 4th O 0 - 5 5 5 0 5 5 4th 4th 0 0 0 2 3 1 1 0 24 4.0 post 5 4th 3 1 O O O 4th 0 5 4th 4th 5 3 2 O 0 0 0 0 0 0 0 5

- 24 names of the test plants from Table III

3 & I70

Sb
Rp
Ct
Sy
Mz
Ww
Rc
Sn sugar beet
Rapeseed
cotton
Soybeans
Corn
Winter wheat
rice
Senecio vulgaris 3 Ip Ipomoea purpurea At the Amaranthus retroflexus pi Polygonum aviculare Approx Chenopodium album Po Portulaca oleracea away Abutilon theophrastii Cv Convolvulus arvensis Ot / Av
Dg as in example 1
Digitaria sanguinalis Pooh
St. Poa annua
Setaria viridis Ec Echinochloa crus-galli Sh Sorghum halepense Ag Agropyron repens Cp Cyperus rotundus example

This example demonstrates the herbicidal properties of Compound No. 1 of Table I against a number of test plants. The tests were generally carried out as described in Example 1, but with a

35 small change in test before germination. In this test, the seeds of the test plants were placed in shallow soil

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sown grooves and leveled and sprayed the surface. Fresh soil was then spread over the sprayed surface in a thin layer. The results obtained were numbered from 0 to 9, where 0 signifies damage of 0 to 11% and 9 signifies complete destruction.

The results are summarized in Tables IV, V and VI below.

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TAB. IV

O LC OO

Application Before or after TEST PLANT FN Ww Br Pe Fb Av Al Sm Approx pi Tm rate (kg / ha) germinated O 0 0 0 0 0 0 3 0 0 1 Pre O 0 1 1 0 1 9 9 9 9 post O 0 0 0 0 0 8th 8th - 2 4th Pre 7th 3 8th 8th 7th 7th 9 9 9 9 post

TAB. V

Application
rate (kg / ha) Before or after
germinated TEST PLANTS Rp Sb Sr To Al Sm Approx Pl Sn Sp 1 Pre 0 5 O 0 0 0 1 0 0 0 1 post 8th 9 6th (Ti 0 (Ti 9 7th 9 9 4th Pre 3 9 3 1 3 7th 5 4th 8th 0 4th post 9 9 9 9 2 9 9 9 9 9

TAB. VI

-ο ο co cc

Application Before or after Sy Ct Mz Rc Sg TEST PLANTS Ec Dg St. Sf Sh Cn At the rate (kg / ha) germinated 0 0 0 0 0 egg 0 0 0 0 0 0 0 1 Pre 1 1 0 0 0 0 0 0 0 0 0 0 7th 1 post 0 0 0 0 0 0 0 0 0 0 0 0 1 4th Pre 1 2 0 7th 1 0 4th 2 2 3 3 1 9 4th post 3

- 29 -

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The results of Table VI relate to the observation 26 days after treatment.

The names of the test plants have been abbreviated as follows in Tables IV, V and VI:

Br
Pe
Fb
Al barley
pea
Field bean
Alopecurus myosuroides Sm Stellaria media pi PolvKonum aviculare Tm Tripleurospermum maritimum inodorum Sr
To
Pl Sunflower
tomato
Polygonum persicaria Sp Sinapis arvensis Sg
egg Sorghum
Eleusine indica Sf Setaria faberii Sh Sorghum halepense

25 Example 4

This example shows the preparation of compound no. 1 of Table I by the method according to Scheme A.

30 3.5 g of 3-amino-5-isopropyl-1,2,4-triazole were in 40 ml of dry pyridine were dissolved and 5.0 g of methyl-N-chlorocarbonyl-N-isopropyl urethane were added dropwise. the Mixture was stirred for two hours at room temperature. The excess pyridine was evaporated in vacuo

35 and the remaining oil taken up in chloroform and washed three times with water (3x50 ml). The chloroform

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solution was dried and evaporated to give a white solid. The compound No. 1 of Table I having a melting point of 156-159 ⁰ C by recrystallization from light petroleum (b.p. 80-100 ⁰ C).

Example 5

This example shows the preparation of compound no. 4 of Table I by the method according to the scheme B.

10 grams of isopropyl isocyanate was added dropwise to a stirred solution of 3-amino-5-methyl-1,2,4-triazole at room temperature (3.92 g) in 50 ml of dry pyridine was added. After the addition was complete, the Solution heated to reflux for 17 hours. The excess pyridine was removed in vacuo and the remaining Solid extracted with aqueous sodium carbonate solution. The aqueous extracts were with 2 molar Hydrochloric acid acidified and the mixture extracted with chloroform. The chloroform extracts were dried and evaporated under reduced pressure. The residue was recrystallized from a mixture of toluene and mineral oil to give Compound No. 4 of Table I with a melting point of 202 ° C.

30 Example 6

This example demonstrates the herbicidal properties of Compound No. 4 of Table I versus a panel of test plants. The tests were carried out as in Example 3 and the results are in Tables VII, VIII and IX combined:

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TAB. VII

-j ο co co

O CD CD ro

Application
rate (kg / ha) Before or after
germinated Ww Br Pe Rp Sb Le TEST PELAN ZEN Al Bt Ag Sm Approx pi Tm Sp 1 Pre 0 0 0 0 2 1 Av 0 0 0 1 2 1 1 1 post 0 0 9 9 9 9 1 2 2 0 9 9 9 9 9 4th Pre 4th 2 8th 9 9 9 8th 5 4th 2 9 7th 9 8th 6th post 7th 2 9 7th 9 9 9 7th 6th 4th 9 9 9 9 9 9

Previous year

ro -ο

-j co

N)

TAB. VIII

O CO OO

Application Before or after Mz Sy Gn Ct To Po TEST PLANTS ip German away Se Co Si Ds Xa rate (kg / ha) germinated 0 0 0 0 0 6th At the 2 3 3 6th 4th 1 1 - 1 Pre 0 8th 0 9 9 9 7th 9 9 9 9 9 9 9 - post 1 8th 0 0 4th 9 9 4th 8th 7th 9 9 8th 8th - 4th Pre 0 9 0 9 9 9 9 9 9 9 9 9 9 9 9 post 9

TAB. IX

Appii
rate cat
(kg ions
/Ha) Vor or Kach
germinated Sy Ct Mz Rc Sg egg TEST PLANTS Dg St. Sf Sh Cp At the Pm O , 75 O O O O O 1 Ec O O O O O 5 2 8th 9 O 2 3 9 1 9 9 9 6th 1 9 8th 3 , 0 5 3 O 3 O 6th 9 8th 8th 5 6th 1 8th 5 cn 9 O 7th 8th 9 7th 9 9 9 9 3 9 9 9

B 8 ^ 70

The abbreviations of the test plant names correspond to the information in Examples 1, 2 and 3 with the following exception:

Bt Bromus tectorum Gn
German Peanut
Desmodium tortuosum Se Sesbania exaltata Co Cassia obtusifolia Si Sida spinosa Ds Datura stramonium Xa Xanthium pennsylvanicum Pm Panicum maximum Example 7

20 This example shows a herbicidal agent in

Form of a dispersible powder with a triazolotriazine according to the invention. The remedy contained that
the following components:

component

Gev.%

Connection No. 4

Vanicell E ^ (a dispersing agent based on lignosulfonate) Fenopon T77®

(a taurate wetting agent)

Citric acid
Spestone (kaolin)

50 5

5 38

7 U y «4 7. ' 0 9 ö

O · ι \ j

- 35 -

This dispersible powder can be used as a suspension be applied in an aqueous solution, the surface-active agent "Span 80" (sorbitan fatty acid ester) in a concentration of 0.2 g / l and "Tween 20" (ethoxylated sorbitan fatty acid ester) in one Contains concentration of 0.8 g / l.

Example 8 10

This example shows a procedure for the preparation of Compound # 24 of Table I.

13.0 g of 3-amino-5-methylthio-1,2,4-triazole were added in portions to a stirred solution of 13.4 g of N-isopropyl-bis [chloroformyl] amine in 150 ml of dry acetonitrile. After the addition was complete, the mixture was refluxed for 6 hours. The reaction mixture was filtered while hot. When standing overnight at ⁰ ° C., a pale yellow solid with a melting point of 260 ^° C., which was identified as compound no.

709847/0982

Claims (13)

Claims 1. Triazolotriazine derivatives of the general formula: R ¹ 10 'R ² in which R is an alkyl or cycloalkyl radical with 1 to 8 Denotes carbon atoms and R denotes a hydrogen atom, an alkyl or cycloalkyl radical with 1 to 6 Carbon atoms, an alkylthio radical with 1 to 6 carbon atoms or a dialkylamino radical, in which the two alkyl radicals each contain 1 to 6 carbon atoms and their salts. 2. Triazolotriazine derivatives according to claim 1, characterized characterized in that R is isopropyl, cyclopropyl or 2
sec-butyl and R for methyl, isopropyl or tert-butyl stands. 3. Triazolotriazine derivatives according to claim 1 or 2, characterized in that R is an isopropyl radical and R stands for an isopropyl or methyl radical. 4. Process for the preparation of a triazolotriazine derivative according to claim 1, characterized in that a 5-substituted 3-amino-1,2,4-triazole of the general Formula: N-N -ΛΑ · ' 709847/0982 OWGINAL INSPECTED B 8170 2720702 2
in which R has the meaning already given, with an N-substituted N-chlorocarbonyl urethane derivative of the general formula: R ¹ 0γ ^Ν γ0 I I 3 Cl OR in which R has the meaning already given and R ^ is a lower alkyl radical or with an N-substituted bis (chlorocarbonyl) compound of the general formula: R ¹ Cl Cl in which R has the meaning already given or at elevated temperature with at least 3 parts by mole of one 1 1 Isocyanates of the general formula R NCO, in which R the has already given meaning, converts and wins the triazolotriazine compound formed. 5. Herbicidal agents, characterized by a content of at least one triazolotriazine compound according to claim 1 together with a solid or liquid Carrier containing 30 diluents. 6. Herbicidal compositions according to claim 5, characterized by the presence of a surface-active agent. 7. Herbicidal agents according to claim 5 or 6, marked 7ü9iU7 / 0982 B 8170 net by a content of an aqueous solution of an alkali metal salt a triazolotriazine derivative according to claim 1. 8. A method for damaging or killing undesirable plants, characterized in that one is applied to the plants or the growth medium of which applies a triazolotriazine derivative according to claim 1. 9. The method according to claim 8, characterized in that there is a triazolotriazine derivative according to claim 2 or 3 applies. 10. The method according to claim 8 or 9, characterized in that the triazolotriazine compound is used as a salt with a cation which is substituted by an ammonium ion, an ammonium ion substituted by 1,2,3 or 4 alkyl radicals each having 1 to 6 carbon atoms, or an alkali metal ion an alkaline earth metal ion and is preferably formed by a sodium or potassium cation . 11. The method according to any one of claims 8 to 10, characterized in that the triazolotriazine derivative is used in amounts of 0.5 to 10 kg / ha. 12. The method according to claim 8 for the selective growth inhibition of weeds in wheat and barley crops, characterized in that one triazolotriazine compound according to a on the area under cultivation of the useful plants of claims 1 to 3 in sufficient amount to inhibit the growth of weeds, but insufficient for one causes substantial damage to the crop. 13. The method according to claim 12, characterized in that the triazolotriazine compound in an amount of Apply 0.5 to 5 kg / ha. 709847/0982